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WO1994005054A1 - Procede d'elimination de cellules accumulatrices au soufre-sodium - Google Patents

Procede d'elimination de cellules accumulatrices au soufre-sodium Download PDF

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Publication number
WO1994005054A1
WO1994005054A1 PCT/EP1993/002181 EP9302181W WO9405054A1 WO 1994005054 A1 WO1994005054 A1 WO 1994005054A1 EP 9302181 W EP9302181 W EP 9302181W WO 9405054 A1 WO9405054 A1 WO 9405054A1
Authority
WO
WIPO (PCT)
Prior art keywords
sulfur
solution
sodium
reaction
acid
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
PCT/EP1993/002181
Other languages
German (de)
English (en)
Inventor
Hartmut Hammer
Dieter Winkler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
SILENT POWER GmbH
Original Assignee
SILENT POWER GmbH
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by SILENT POWER GmbH filed Critical SILENT POWER GmbH
Priority to JP50589494A priority Critical patent/JPH08500465A/ja
Priority to DE59301652T priority patent/DE59301652D1/de
Priority to EP19930919069 priority patent/EP0656154B1/fr
Publication of WO1994005054A1 publication Critical patent/WO1994005054A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/54—Reclaiming serviceable parts of waste accumulators
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/30—Destroying solid waste or transforming solid waste into something useful or harmless involving mechanical treatment
    • B09B3/35—Shredding, crushing or cutting
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B09—DISPOSAL OF SOLID WASTE; RECLAMATION OF CONTAMINATED SOIL
    • B09B—DISPOSAL OF SOLID WASTE NOT OTHERWISE PROVIDED FOR
    • B09B3/00—Destroying solid waste or transforming solid waste into something useful or harmless
    • B09B3/70—Chemical treatment, e.g. pH adjustment or oxidation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/02—Preparation of sulfur; Purification
    • C01B17/06—Preparation of sulfur; Purification from non-gaseous sulfides or materials containing such sulfides, e.g. ores
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B17/00—Sulfur; Compounds thereof
    • C01B17/16—Hydrogen sulfides
    • C01B17/165—Preparation from sulfides, oxysulfides or polysulfides
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D1/00—Oxides or hydroxides of sodium, potassium or alkali metals in general
    • C01D1/04—Hydroxides
    • C01D1/20—Preparation by reacting oxides or hydroxides with alkali metal salts
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F11/00—Compounds of calcium, strontium, or barium
    • C01F11/46—Sulfates
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
    • Y02W30/00—Technologies for solid waste management
    • Y02W30/50—Reuse, recycling or recovery technologies
    • Y02W30/84—Recycling of batteries or fuel cells

Definitions

  • the invention relates to a method for the disposal of sodium-sulfur storage cells.
  • Embed 225 memory cells in wax-like materials such as paraffin remove the sodium by melting and remove and recycle the sulfur electrodes and the housing materials separately.
  • the battery or individual cells are mechanically shredded by shredding or the like. To prevent oxidation, this can be done under inert gas or vacuum or, preferably, under water.
  • inert gas or vacuum or, preferably, under water.
  • water has the advantage that the exothermic reaction of the sodium metal which may still be present can be trapped and thus the comminution device, e.g. the shredder spared
  • REPLACEMENT LEAF becomes. Furthermore, the dissolving process is started as soon as it is crushed, which saves time.
  • the hydrogen produced can be used for heating purposes.
  • the crushing should produce parts of 0.1 cm to 5 cm, preferably about 1 cm.
  • the dissolving reaction of the polysulfide and the solid sulfur can take place in a temperature interval from room temperature to 200 ° C., preferably at 120 ° C.
  • a temperature interval from room temperature to 200 ° C., preferably at 120 ° C.
  • the entire polysulfide formed from the solid sulfur can be oxidized to sulfate by adding an oxidizing agent without transferring the solution to another reactor.
  • Hydrogen peroxide is preferably used for the oxidation.
  • the pH must always be kept above pH8 during the reaction. Lye, preferably sodium hydroxide, is used for this. After the liquid has been separated off, the residue is washed with water.
  • the wash water is used in the dissolving process.
  • the washed solids can be separated into metals and non-metals if recycling of the components is economically justifiable. In the other case, problem-free disposal, e.g. Landfill, possible.
  • the salt solution can be disposed of or recycled directly or after evaporation, with the water being fed back into the washing or dissolving process.
  • REPLACEMENT LEAF Comminution, dissolving and separating process take place, as well as the treatment of the solid residue, as described under l.
  • the solution is reacted with acid, preferably sulfuric acid, and oxidizing agent, preferably hydrogen peroxide.
  • acid preferably sulfuric acid
  • oxidizing agent preferably hydrogen peroxide.
  • the reaction temperature can be from room temperature to 150 ° C., preferably at the end of the exothermic reaction at 120 ° C. Elemental sulfur is formed in the process.
  • the resulting hydrogen sulfide is oxidized to sulfate in situ. If the temperature is kept above the melting point of sulfur, a phase of liquid sulfur quickly forms, which can be easily removed, cleaned and recycled in liquid form.
  • the solution and solids are disposed of as in 1.
  • the solution is treated with acid, preferably sulfuric acid. This process produces sulfur, which is withdrawn as in FIG. 2. Hydrogen sulfide formed in parallel is drained off, boiled out or stripped with gas, preferably nitrogen. It is used as a chemical or converted to further sulfur in a Claus plant. This sulfur may be cleaned together with the extracted sulfur.
  • the saline and solids are disposed of as in 1.
  • the process variants have in common that the memory cells are first crushed in the presence of water and the soluble constituents of the electrical element are dissolved to form a sodium polysulfide solution. At the same time or afterwards, preferably sodium hydroxide solution or sulfuric acid is added, whereby sodium sulfate is wholly or partly formed.
  • the structural components of the cell i.e. Cell wall, electrodes, ceramics etc. can be separated at any time as soon as Na polysulfide is dissolved.
  • the amount of sodium sulfate formed can be increased by adding aqueous hydrogen peroxide solution. Hydrogen sulfide is converted together with H 2 O2 solution to sulfur and / or sulfate. Sodium salt can form as a uniform product, which is evaporated in a known manner, if necessary purified and crystallized.
  • Sulfuric acid together with H 2 O 2 solution requires considerably less peroxide than alkaline oxidation and allows sodium sulfate to be formed in addition to elemental sulfur, and the sulfur can be separated off. Sodium sulfate and sulfur are to be cleaned in a known manner.
  • Na 2 S0 4 sulfur and hydrogen sulfide, hydrogen sulfide being driven off and oxidized to elemental sulfur, for example in a Claus plant.
  • Na S0 4 and primarily formed sulfur can be separated, as described above.
  • the crushing of batteries or individual cells is carried out with crushing or cutting systems, expediently by shredding under water or with sprinkling with water, provided that the gas space is rendered inert. This should result in parts of 0.1 to 5 cm, preferably 0.2 to 2 cm in diameter. Residues of sodium from cells that are not fully discharged are rendered harmless by water. The resulting hydrogen can be removed.
  • the dissolution reaction of the Na polysulfide begins, which is continued with liquid movement at temperatures between room temperature and 200 ° C., preferably at 80 to 120 ° C., after being transferred to a reactor.
  • the dissolution rate of Na polysulfide is increased by elevated temperature and is about 10 min at 80 ° C in one example. Saturated solutions of about 260 g / 1 with a medium composition of Na 2 & 2 ⁇ are achieved with water.
  • Utilization of the active substances sodium / sulfur are preferably carried out in a reactor.
  • the reactor is preferably a closed reactor, equipped with adding device, gas discharge, bottom drain,
  • the reactor is expediently increased
  • the reaction is preferably monitored by
  • Solution can also under acidic conditions, preferably under
  • 120 ° C can be used.
  • the sulfur can form at 120 ° C
  • Hydrogen sulfide can be used at elevated temperatures
  • Inert gases such as nitrogen are expelled and in one
  • Claus plant can be oxidized to sulfur in the usual way with atmospheric oxygen. This variant is suitable for the location of a Claus plant and for the disposal of large quantities of storage cells. Only one mole of H 2 S0 4 is used per mole of Na 2 S 7 .
  • a solution of 20 g (0.15 mol) of sodium polysulfide is prepared from used Na-S storage cells by adding water and the solid components of the cell are removed.
  • a mixture of 14.7 g (0.15 mol) of sulfuric acid in 5.1 g (0.15 mol) of hydrogen peroxide as a 30% (m / m) solution is added with stirring.
  • the sealed reactor is then heated to 120 ° C.
  • the precipitated sulfur melts and forms droplets that collect on the reactor floor.
  • the sulfur can be removed. 21.5 g (0.15 mol) of sodium sulfate and 13 g (0.4 mol) of sulfur are obtained.
  • Hydrogen sulfide is obtained in an amount of 5.1 g (0.15 mol).

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Inorganic Chemistry (AREA)
  • Environmental & Geological Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Toxicology (AREA)
  • General Health & Medical Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Electrochemistry (AREA)
  • Processing Of Solid Wastes (AREA)
  • Secondary Cells (AREA)
  • Fertilizers (AREA)

Abstract

On élimine et recycle des cellules accumulatrices au soufre-sodium en broyant les cellules en présence d'eau, en séparant les matières résiduelles solides et en préparant une solution aqueuse de polysulfure de sodium. Par des variations de la réaction, on peut traiter de manière très rentable les produits obtenus en réduisant au minimum la quantité de produits secondaires.
PCT/EP1993/002181 1992-08-20 1993-08-16 Procede d'elimination de cellules accumulatrices au soufre-sodium Ceased WO1994005054A1 (fr)

Priority Applications (3)

Application Number Priority Date Filing Date Title
JP50589494A JPH08500465A (ja) 1992-08-20 1993-08-16 ナトリウム−硫黄蓄電池の処理方法
DE59301652T DE59301652D1 (de) 1992-08-20 1993-08-16 Verfahren zur entsorgung von natrium-schwefel-speicherzellen
EP19930919069 EP0656154B1 (fr) 1992-08-20 1993-08-16 Procede d'elimination de cellules accumulatrices au soufre-sodium

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DEP4227511.3 1992-08-20
DE4227511A DE4227511C1 (fr) 1992-08-20 1992-08-20

Publications (1)

Publication Number Publication Date
WO1994005054A1 true WO1994005054A1 (fr) 1994-03-03

Family

ID=6465925

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP1993/002181 Ceased WO1994005054A1 (fr) 1992-08-20 1993-08-16 Procede d'elimination de cellules accumulatrices au soufre-sodium

Country Status (6)

Country Link
EP (1) EP0656154B1 (fr)
JP (1) JPH08500465A (fr)
AT (1) ATE134280T1 (fr)
CA (1) CA2141575A1 (fr)
DE (2) DE4227511C1 (fr)
WO (1) WO1994005054A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE4419695C1 (de) * 1994-06-04 1995-08-10 Fraunhofer Ges Forschung Verfahren zum Lösen der Wirkstoffe von Alkali-Metall-Batterien
JP2980844B2 (ja) * 1996-06-11 1999-11-22 東京電力株式会社 ナトリウム−硫黄電池からのＮａ回収方法
DE19906879B4 (de) * 1999-02-19 2014-03-27 Datasec Electronic Gmbh Elektronisches Schließ- und Überwachungssystem
EP2662329A1 (fr) * 2012-05-11 2013-11-13 Creachem SA Compositions à libération de peroxygène et leur procédé de production
JP6476598B2 (ja) 2014-06-03 2019-03-06 三菱マテリアル株式会社 ナトリウム−硫黄電池からナトリウムを回収する方法、ナトリウム−硫黄電池からナトリウムを回収する装置
KR102134719B1 (ko) * 2018-11-07 2020-07-16 주식회사 티에스케이프리텍 폐리튬이온배터리의 재활용 장치 및 방법

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0413275A1 (fr) * 1989-08-18 1991-02-20 Asea Brown Boveri Aktiengesellschaft Procédé de traitement des éléments d'accumulateurs
US5015541A (en) * 1990-03-15 1991-05-14 Eveready Battery Company, Inc. Process for neutralizing sulfur-containing cells
EP0433654A2 (fr) * 1989-12-22 1991-06-26 Degussa Aktiengesellschaft Procédé pour la récupération de polysulphure de natrium de batteries en natrium/soufre usées

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
IT1237502B (it) * 1989-10-26 1993-06-08 Nuova Samin Spa Procedimento per il trattamento di pile esauste

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0413275A1 (fr) * 1989-08-18 1991-02-20 Asea Brown Boveri Aktiengesellschaft Procédé de traitement des éléments d'accumulateurs
DE3927225A1 (de) * 1989-08-18 1991-02-21 Asea Brown Boveri Verfahren zur entsorgung von speicherzellen
EP0433654A2 (fr) * 1989-12-22 1991-06-26 Degussa Aktiengesellschaft Procédé pour la récupération de polysulphure de natrium de batteries en natrium/soufre usées
US5015541A (en) * 1990-03-15 1991-05-14 Eveready Battery Company, Inc. Process for neutralizing sulfur-containing cells

Also Published As

Publication number Publication date
DE59301652D1 (de) 1996-03-28
JPH08500465A (ja) 1996-01-16
DE4227511C1 (fr) 1993-07-22
EP0656154B1 (fr) 1996-02-14
ATE134280T1 (de) 1996-02-15
EP0656154A1 (fr) 1995-06-07
CA2141575A1 (fr) 1994-03-03

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